Water-soluble monoazodye containing a triazinyl or pyrimidinyl group and at least one vinyl sulfonyl type group in its structure

ABSTRACT

A water-soluble monoazodye having the following formula (I) in its free acid form: ##STR1## wherein X is --CH═CH 2  or --CH 2  CH 2  W wherein W is a leaving group removable by alkali; R 1  is methyl, --NHCONH 2  or --NHCOT 1  wherein T 1  is methyl, ethyl, --CH 2  CH 2  COOH or --CH═CHCOOH; R 2  is hydrogen, lower alkyl or lower alkoxy; and Z is ##STR2## wherein P is cyano or halogen, each of Q and U which are independent of each other, is halogen, V is halogen or ##STR3## and Y is halogen or a group of the following formula (1) or (2): ##STR4## wherein R 3 , A, R 4  and E are as defined in the disclosure and G is as defined above, has a moderate yellow to orange color and is particularly suitable for dyeing cellulose fibers or nitrogen-containing fibers.

This present invention relates to a water-soluble monoazodye of amoderate yellow color having a novel chemical structure. Particularly,it relates to a water-soluble monoazodye having from 2 to 4 reactivegroups in the chemical structure and being particularly suitable fordyeing cellulose fibers or nitrogen-containing fibers.

It is common to use water-soluble reactive dyes to dye fibers containingcellulose fibers or nitrogencontaining fibers. Such water-solublereactive dyes are required to be excellent in level dyeing and capableof dyeing the objects in deep color, and yet the dyed products arerequired to be excellent in various fastnesses. These properties ofreactive dyes delicately differ depending upon the basic structures,substituents or reactive groups of the dyes or depending upon thecombination thereof. Therefore, dyes having various chemical structureshave been proposed.

Japanese Examined Patent Publications No. 18474/1983 and No. 18471/1983disclose reactive dyes having the following structural formulas (A) and(B), as examples of dyes of moderate yellow type: ##STR5##

In each of these reactive dyes, the diazo component is a component of anaphthalene type, but these reactive dyes are still slightly inadequatein the level dyeing property, and they are not fully satisfactory alsoin the build-up property.

The present invention has been made in view of the above problems, andit is an object of the present invention to provide a water-solublemonoazodye useful as a reactive dye of moderate yellow to orange typewhich is excellent not only in the chlorine fastness and light fastnessbut also in the level dyeing property and which is also excellent in thebuild-up property.

As a result of extensive studies, the present inventors have found itpossible to accomplish the above object by using a novel monoazocompound having a specific chemical structure. The present invention hasbeen accomplished on the basis of this discovery.

Thus, the present invention provides a water-soluble monoazodye havingthe following formula (I) in its free acid form: ##STR6## wherein X is13 CH═CH₂ or --CH₂ CH₂ W wherein W is a leaving group removable byalkali; R¹ is methyl, --NHCONH₂ or --NHCOT¹ wherein T¹ is methyl, ethyl--CH₂ CH₂ COOH or --CH═CHCOOH; R² is hydrogen, lower alkyl or loweralkoxy; and Z is ##STR7## wherein P is cyano or halogen, each of Q and Uwhich are independent of each other, is halogen, V is halogen or##STR8## and Y is halogen or a group of the following formula (1) or(2): ##STR9## wherein R³ is hydrogen or lower alkyl, A is a C₁ -C₄ alkylor naphthalene group substituted by at least one selected from the groupconsisting of a sulfonic acid group and a carboxylic acid group, orphenyl substituted by at least one selected from the group consisting ofa sulfonic acid group and a carboxylic acid group, and which may besubstituted by at least one selected from the group consisting ofhydroxyl, halogen, C₁ -C₂ alkyl and C₁ -C₂ alkoxy, R₄ is hydrogen or C₁-C₄ alkyl, E is phenylene unsubstituted or substituted by lower alkyl,lower alkoxy, halogen or a sulfonic acid group, a naphthalene groupunsubstituted or substituted by a sulfonic acid group, C₁ -C₄ alkyleneor C₁ -C₄ alkyleneoxy C₁ -C₄ alkylene, and X is as defined above.

In the above water-soluble monoazodye of the present invention, X in theformula (I) represents --CH═CH₂ or --CH₂ CH₂ W. However, when X is --CH₂CH₂ W, it will be converted to --CH═CH₂ by the removal of W-H by alkali.Thus, these two groups may be regarded as equivalent.

The group represented by W which is removable by the action of alkali,may, for example, be a sulfuric acid ester group, a thiosulfuric acidester group, a phosphoric acid ester group, an acetic acid ester groupor a halogen atom. Particularly preferred is a sulfuric acid estergroup.

Y in the formula (I) is halogen or a group of the above formula (1) or(2).

When Y is halogen, the halogen includes fluorine, chlorine and bromine.However, when V is halogen, Y is preferably chlorine, and when V is##STR10##

Y is preferably fluorine.

When Y is the group of the above formula (1), R₄ is hydrogen or C₁ -C₄alkyl, preferably hydrogen, methyl or ethyl.

W in the group Y has the same meaning as the leaving group removable byalkali described above. W in the group X and W in the group Y may be thesame or different.

When P, Q or u is halogen, such halogen includes fluorine, chlorine andbromine, preferably chlorine and fluorine.

Specific examples of ##STR11## include: ##STR12##

Particularly preferred are: ##STR13##

The halogen for V in the formula (I) includes fluorine, chlorine andbromine. However, when Y is halogen, V is preferably chlorine, and whenY is other than halogen, V is preferably chlorine or fluorine.

Specific examples of the group ##STR14## wherein A is a C₁ -C₄ alkyl ornaphthalene group substituted by at least one selected from the groupconsisting of a sulfonic acid group and a carboxylic acid group, includethe following groups: ##STR15##

Specific examples of the same group wherein A is phenyl substituted byat least one selected from the group consisting of a sulfonic acid groupand a carboxylic acid group, and which may be substituted by at leastone selected from the group consisting of hydroxyl, halogen, C₁ -C₂alkyl and C₁ -C₂ alkoxy, include the following groups: ##STR16##

Among them, the following groups are particularly preferred for##STR17## when Y is halogen: ##STR18##

For E, the phenylene unsubstituted or substituted by lower alkyl, loweralkoxy, halogen or a sulfonic acid group and the naphthalene groupunsubstituted or substituted by a sulfonic acid group include thefollowing groups: ##STR19##

In the above formulas, the bond indicated by * is the bond which isconnected to the ##STR20## group. Further, the C₁ -C₄ alkylene or the C₁-C₄ alkyleneoxy C₁ -C₄ alkylene for E may, for example, be the followinggroups:

β-(β-chloroethylsulfonyl)ethyl,

γ-(β-chloroethylsulfonyl)propyl,

δ-(β-chloroethylsulfonyl)butyl,

γ-(β-sulfatoethylsulfonyl)propyl,

β-(vinylsulfonyl)ethyl,

β-[β-(β-chloroethylsulfonyl)ethoxy]ethyl,

γ-[γ-(β-sulfatoethylsulfonyl)propoxy]propyl, and

β-[β-(vinylsulfonyl)ethoxy]ethyl.

When V is halogen, ##STR21## is preferably a group wherein R₄ ishydrogen and E is phenylene, C₁ -C₄ alkylene or C₁ -C₄ alkyleneoxy C₁-C₄ alkylene, such as ##STR22##

In the formula (I), R¹ is methyl, --NHCONH₂ or --NHCOT¹ wherein T¹ ismethyl, ethyl, --CH₂ CH₂ COOH or --CH═CHCOOH. The monoazodye wherein R¹is --NHCONH₂ is particularly excellent in that an object dyed therewithundergoes no color change even against a strong alkaline aqueoussolution at the time of the post mercerizing treatment, and that it hasno thermotropy.

Further, when Z is ##STR23## wherein P, Q and U are as defined above##STR24## wherein each of V' and Y' is halogen, R¹ is preferably--NHCOCH₂ CH₂ COOH or --NHCOCH═CH₂ COOH with a view to improvement ofthe solubility of the dye.

For R², the lower alkyl is preferably methyl or ethyl, and the loweralkoxy is preferably methoxy or ethoxy.

For R³, the lower alkyl is usually methyl or ethyl.

In the water-soluble monoazodye of the present invention, --SO₃ H and--SO₂ X in the diazo component in the above formula (I) may besubstituted at any positions of the o-, m- and p-positions. It ispreferred that one of them is located at the p-position and the other islocated at the o-position.

The water-soluble monoazodye of the present invention may be used in thefree acid form or in the form of its salt. The salt may, for example, bean alkali metal salt or an alkaline earth metal salt. Particularlypreferred is a lithium salt, a sodium salt or a potassium salt.

The most preferred dyes of the present invention are represented by thefollowing formulas (I-a), (I-b) and (z-c). ##STR25## wherein X' and R² 'have the same meanings as the above X and R², respectively, A' is##STR26## and Y' is fluorine or chlorine. ##STR27## wherein X" and R² "have the same meanings as the above X and R² respectively, R¹ " is.[.--NHCH₂ CH₂ COOH or --NHCH═CHCOOH .]. .Iadd.NHCOCH₂ CH₂ COOH or--NHCOCH═CHCOOH.Iaddend., and V" is fluorine or chlorine. ##STR28##wherein X'" and R² '" have the same meanings as the above X and R²,respectively, R¹ '" is .[.--NHCH₂ CH₂ COOH or --NHCH═CHCOOH.]..Iadd.NHCOCH₂ CH₂ COOH or --NHCOCH═CHCOOH.Iaddend., and when P'" ischlorine, each of Q'" and U'"is fluorine, and when P'" is cyano, each ofQ'" and .[.Q'".]. .Iadd.U'".Iaddend. is chlorine.

The water-soluble monoazodye of the present invention can be produced asfollows.

Namely, an azo compound of the following formula (II): ##STR29## whereinR¹, R² and X are as defined above, is condensed with a reactive compoundof the following formula (III):

    Z.sup.1 --Hal                                              (III)

wherein Z¹ is ##STR30## wherein P, Q and U are as defined above or##STR31## wherein Hal is halogen, and Hal is halogen in an aqueousmedium at a temperature of from 0° to 15° C., whereby a water-solublemonoazodye of the following formula (IV): ##STR32## wherein R¹, R², Xand Z¹ are as defined above, is produced.

In a case where Z in the formula (I) is ##STR33## wherein one of V or Yis halogen, an azo compound of the following formula (V): ##STR34##wherein R¹, R², X and Hal are as defined above, is condensed with anamine of the following formula (VI), (VII) or (VIII): ##STR35## whereinR³, R⁴, A, E and X are as defined above, in an aqueous medium at atemperature of from 30 to 40° C., whereby a water-soluble monoazodye ofthe following formula (IX) is obtained: ##STR36## wherein R¹, R² are asdefined above, and when y² is halogen, V² is ##STR37## when y² is thegroup of the formula (1) or (2), V² is halogen.

Further, to produce a water-soluble monoazodye of the formula (I)wherein V is ##STR38## and Y is the group of the formula (1) or (2), amonoazodye of the following formula (X): ##STR39## wherein R¹, R², R³, Aand X are as defined above, and y³ is halogen, is condensed with anamino compound of the above formula (VII) or (VIII) in an aqueous mediumat a temperature of from 85° to 95° C. at a pH of from 4 to 6.

The feature in the chemical structure of the water-soluble monoazodye ofthe present invention resides in that the diazo component has a phenylgroup substituted by --SO₃ H and --SO₂ X and the coupling component hasa halotriazinyl group, a pyrimidinyl group or a triazinyl groupsubstituted by the group of the formula (1) or (2). By virtue of thischaracteristic chemical structure, the build-up property and the leveldyeing property at the time of dyeing are remarkably improved.

The water-soluble monoazodye of the present invention can be widely usedas a dyestuff for dyeing fibers and cloths, a colorant for tinting paperand synthetic resins and as a colorant for e.g. an ink for an ink jetprinter. However, it is particularly suitable for use as a dyestuff.

When the water-soluble monoazodye of the present invention is to be usedas a dyestuff, the fibers to be dyed may, for example, be cellulosefibers such as cotton, viscose rayon, cupra ammonium rayon or kemp, ornitrogen-containing fibers such as polyamide, wool or silk. Particularlypreferred are cellulose fibers. Such fibers may be used in the form ofmixed fibers with e.g. polyester, triacetate or polyacrylonitrile.

To dye cellulose fibers or nitrogen-containing fibers by means of thewater-soluble monoazodye of the present invention, it is common toemploy an acid-binding agent, for example, an inorganic alkali such assodium hydrogencarbonate or sodium carbonate, or an organic base such astriethylamine. The dyeing can be conducted in the presence of such anacid-binding agent in accordance with a conventional method.

The water-soluble monoazodye of the present invention may be used incombination with the other water-soluble dye.

As the dyeing method, a dipping method is particularly preferred, andthe dyeing temperature is usually from 40° to 80° C.

Further, the water-soluble monoazodye of the present invention can beapplied also to other dyeing method such as a cold pad batch method, apad steam method, or a textile printing method.

The water-soluble monoazodye of the formula (I) of the present inventionis particularly suitable for dyeing cellulose fibers ornitrogen-containing fibers to a yellow to orange color, and it isexcellent in the buildup property. Further, the dyed products areexcellent not only in the chlorine-fastness and the light-fastness butalso in the level dyeing property.

Now, the present invention will be described in further detail withreference to Examples. However, it should be understood that the presentinvention is by no means restricted to such specific Examples.

EXAMPLE 1 AND COMPARATIVE EXAMPLE 1

0.3 g or 1.2 g of each of monoazodyes of the following formulas (I-1)and (C): ##STR40## was dissolved in 300 ml of water, and 20 9 ofGlauber's salt was added thereto to obtain a dye bath. In this dye bath,15 9 of a non-mercerized cotton cloth was dipped, and the temperaturewas raised to 60° C. over a period of 30 minutes. Then, 4.5 9 of sodiumcarbonate was added thereto, and dyeing was conducted at 60° C. for onehour, followed by washing with water, soaping, washing with water anddrying to obtain a yellow dyed cloth.

Here, the monoazodye of the above formula (I-1) was prepared by reacting1 mol of a monoazo compound of the following formula (II-1): ##STR41##with 1 mol of 3-sulfoaniline in an aqueous medium at 35° C. for 4 hourswhile maintaining the pH at a level of from 5.0 to 5.5, followed bysalting out with potassium chloride. [max: 404 nm (water)]

Measurement of the build-up property

With respect to each dyed cloth, its surface reflectance was measured bya color difference meter (Macbeth® spectrometer MS-2020, manufactured bya division of Kolmorgen Corporation) to obtain a percentage exhaustion.The build-up property was represented by a relative value of the dyeddensity obtained by using 1.2 g of the dye to the dyed density obtainedby using 0.3 g of the dye.

Level dyeing property

With respect to the dyed cloth obtained by using 0.3 g of eachmonoazodye, the uniformity in dyeing was visually evaluated.

The results are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                                        Build-up                                                                      property    Level dyeing                                              Monoazodye                                                                            (1.2 g/0.3 g)                                                                             property                                          ______________________________________                                        Example 1 (I-1)     250         Remarkably                                                                    uniformly dyed                                Comparative                                                                             (C)       150         Non-uniformity in                             Example 1                       the dyed density                                                              observed                                      ______________________________________                                    

EXAMPLE 2

0.3 g or 0.6 g of a monoazodye [max: 412 nm (water)] of the followingformula (I-2): ##STR42## was dissolved in 300 ml of water, and 20 g ofGlauber's salt was added thereto to obtain a dye bath. In this dye bath,15 g of a cotton cloth was dipped, and the temperature was raised to 60°C. over a period of 30 minutes. Then, 4.5 g of sodium carbonate wasadded thereto, and dyeing was conducted at 60° C. for one hour, followedby washing with water, soaping, washing with water and drying to obtaina yellow dyed product having a good level dyeing property. Further, thebuild-up property was also good.

Here, the monoazodye of the above formula (I-2) was prepared as follows.

Namely, 1 mol of a monoazodye of the above formula (II-1) was reactedwith 1 mol of 2-aminoethane sulfonic acid in an aqueous medium at atemperature of from 30 to 40° C. under stirring for 10 hours whilemaintaining the pH at a level of 8 with sodium carbonate to obtain acompound of the following formula: ##STR43## Then, this compound wasreacted with 1.2 mol of 3-(βhydroxyethyl)sulfonylaniline sulfuric acidester in an aqueous medium at a temperature of from 90 to 95° C. understirring for 10 hours while maintaining the pH at a level of from 5 to 6with sodium acetate, followed by salting out with potassium chloride toobtain the monoazodye of the above formula (I-2).

EXAMPLE 3

The monoazodyes shown in the following Tables 2 and 3 (in their freeacid forms) were prepared in accordance with the method of Example 1 or2, and cotton cloths were dyed with them in the same manner as inExample 1, whereby their level dyeing properties were excellent, andtheir build-up properties were also excellent.

    TABLE 2       -  (I)      ##STR44##       No.      ##STR45##      --R.sup.1 --R.sup.2 --Y --V max nm (Water) Color of dyed cloth       3-1      ##STR46##      --NHCONH.sub.2 --H --F      ##STR47##      405 Yellow     3-2      ##STR48##      --NHCONH.sub.2 --H --Cl      ##STR49##      405 Yellow     3-3      ##STR50##      --NHCONH.sub.2 --H --Cl      ##STR51##      405 Yellow     3-4      ##STR52##      --NHCONH.sub.2 --H --F --NHC.sub.2 H.sub.4 SO.sub.3 H 408 Yellow                                                                       3-5      ##STR53##      --NHCONH.sub.2 --H      ##STR54##      ##STR55##      413 Yellow     3-6      ##STR56##      --NHCONH.sub.2 --H      ##STR57##      --NHC.sub.3 H.sub.6 SO.sub.3      H 415 Yellow                                  3-7      ##STR58##      --NHCONH.sub.2 --H --Cl      ##STR59##      408 Yellow     3-8      ##STR60##      --NHCOCH.sub.2 --CH.sub.3 --F      ##STR61##      410 Yellow     3-9      ##STR62##      --NHCONH.sub.2 --OCH.sub.3 --Cl      ##STR63##      432 Orange     3-10      ##STR64##      --NHCOC.sub.2      H.sub.5 --OCH.sub.3 --F     ##STR65##      428 Yellow     3-11      ##STR66##      --NHCONH.sub.2 --H --Cl      ##STR67##      403 Yellow     3-12      ##STR68##      --NHCONH.sub.2 --H --F      ##STR69##      403 Yellow     3-13      ##STR70##      --NHCONH.sub.2 --OCH.sub.3      ##STR71##      ##STR72##      430 Orange     3-14      ##STR73##      --NHCONH.sub.2 --H --F      ##STR74##      407 Yellow     3-15      ##STR75##      --NHCONH.sub.2 --H --Cl      ##STR76##      405 Yellow     3-16      ##STR77##      --NHCONH.sub.2 --H --Cl      ##STR78##      403 Yellow     3-17      ##STR79##      --NHCONH.sub.2 --H --Cl      ##STR80##      402 Yellow     3-18      ##STR81##      --NHCONH.sub.2 --H --F      ##STR82##      402 Yellow     3-19      ##STR83##      --CH.sub.3 --H --Cl      ##STR84##      391 Yellow     3-20      ##STR85##      --CH.sub.3 --OCH.sub.3 --F      ##STR86##      418 Yellow     3-21      ##STR87##      --NHCONH.sub.2 --H --Cl      ##STR88##      403 Yellow     3-22      ##STR89##      --NHCONH.sub.2 --H --Cl      ##STR90##      403 Yellow     3-23      ##STR91##      --NHCONH.sub.2 --H --F      ##STR92##      403 Yellow     3-24      ##STR93##      --NHCONH.sub.2 --H --NHC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 Cl      ##STR94##      417 Yellow     3-25      ##STR95##      --NHCOCH.sub.2 CH.sub.2      COOH --OCH.sub.3 --Cl --Cl 420 Yellow                             3-26      ##STR96##      --NHCOCH═CHCOOH H --NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2     C.sub.2 H.sub.4 OSO.sub.3      H --F 409 Yellow                              3-27      ##STR97##      --NHCONH.sub.2 H --NHC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3       H      ##STR98##      419 Yellow     3-28      ##STR99##      --NHCOCH.sub.3 --OC.sub.2      H.sub.5     ##STR100##      --Cl 429 Orange     3-29      ##STR101##      --NHCONH.sub.2 --H      ##STR102##      --Cl 407 Yellow     3-30      ##STR103##      --NHCONH.sub.2 --H      ##STR104##      --F 413 Yellow     3-31      ##STR105##      --NHCONH.sub.2 --H      ##STR106##      --NHC.sub.2 H.sub.4 SO.sub.3      H 414 Yellow                                  3-32      ##STR107##      --NHCONH.sub.2 --H      ##STR108##      ##STR109##      412 Yellow     3-33      ##STR110##      --NHCONH.sub.2 --H      ##STR111##      ##STR112##      414 Yellow     3-34      ##STR113##      --NHCOCH.sub.2 --CH.sub.2      COOH --CH.sub.3     ##STR114##      --Cl 411 Yellow     3-35      ##STR115##      --CH.sub.3 H      ##STR116##      ##STR117##      433 Orange     3-36      ##STR118##      --NHCOCH.sub.3 OCH.sub.3 --NHC.sub.2 H.sub.4 SO.sub.2 CH═CH.sub.2      ##STR119##      432 Orange     3-37      ##STR120##      --NHCONH.sub.2 H      ##STR121##      --Cl 402 Yellow     3-38      ##STR122##      --NHCOCH.sub.2 --CH.sub.2      COOH OCH.sub.3 Cl Cl 413 Yellow                               3-39      ##STR123##      --NHCOCH.sub.2 --CH.sub.2      COOH --OCH.sub.3     ##STR124##      --F 426 Orange     3-40      ##STR125##      --NHCOCH═CHCOOH --OCH.sub.3      ##STR126##      ##STR127##      434 Orange     3-41      ##STR128##      --NHCOCH═CHCOOH --OCH.sub.3      ##STR129##      --F 425 Orange     3-42      ##STR130##      --NHCOCH.sub.3 --OCH.sub.3 --NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4     SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3      H --F 423 Orange

                                      TABLE 3                                     __________________________________________________________________________                                                          (I)                                                                             #STR131##                -                                                                            No.                                                                                                                              #STR132##                                                                   --R.sup.1 --R.sup.2                                                           --P --Q --U max nm                                                            (water) Color of  dyed                                                        cloth                      __________________________________________________________________________      3-43                                                                                                                             #STR133##                                                                   --NHCOCH═CHCOOH                                                           --OC.sub.2 H.sub.5                                                            --Cl --F --F 422                                                              Yellow                        - 3-44                                                                                                                          --NHCOCH.sub.2                                                              --CH.sub.2 COOH                                                               --OC.sub.2 H.sub.5                                                            --CN Cl --Cl 423                                                              Yellow                        - 3-45                                                                                                                          --NHCOCH.sub.2                                                              --CH.sub.2 COOH                                                               --OCH.sub.3 --Cl --F                                                          --F 420 Yellow                                                                  - 3-46                                                                        --NHCOCH═CHCOOH                                                         --OCH.sub.3 --Cl --Cl                                                         --Cl 421 Yellow            __________________________________________________________________________

What is claimed is: .[.1. A water-soluble monoazo dye having thefollowing formula (I) in its free acid form: ##STR137## wherein X is--CH═CH₂ or --CH₂ CH₂ W wherein W is a leaving group removable byalkali, R¹ is methyl, --NHCONH₂, or --NHCOT¹ wherein T¹ is methyl,ethyl, --CH₂ CH₂ COOH or --CH═CHCOOH; R² is hydrogen, lower alkyl orlower alkoxy; and ##STR138## wherein V is halogen or ##STR139## Y ishalogen or a group of the following formula (1) or (2): ##STR140##wherein R³ is hydrogen or lower alkyl, A is a C₁ -C₄ alkyl ornaphthalene group substituted by at least one selected from the groupconsisting of a sulfonic acid group and a carboxylic acid group, orphenyl substituted by at least one selected from the group consisting ofa sulfonic acid group and a carboxylic acid group, and which may besubstituted by at least one selected from the group consisting ofhydroxyl, halogen, C₁ -C₂ alkyl and C₁ -C₂ alkoxy, R₄ is hydrogen or C₁-C₄ alkyl, E is phenylene unsubstituted or substituted by lower alkyl,lower alkoxy, halogen or a sulfonic acid group, a naphthalene groupunsubtituted or substituted by a sulfonic acid group, C₁ -C₄ alkylene orC₁ -C₄ alkyleneoxy C₁ -C₄ alkylene, and X is as defined above..].2. Awater-soluble monoazo dye having the following formula (I) in its freeacid form: ##STR141## wherein X is --CH═CH₂ or --CH₂ CH₂ W wherein W isa leaving group removable by alkali; R¹ is --NHCOT¹ wherein T¹ is --CH₂CH₂ COOH or --CH═CHCOOH; R² is hydrogen, lower alkyl or lower alkoxy;and Z is ##STR142## wherein P is cyano or halogen, each of Q and U whichare independent of each other, is halogen. .[.3. The monoazo dyeaccording to claim 1, wherein V is ##STR143##.[.4. The monoazo dyeaccording to claim 1, wherein V is .[.5. The monoazo dye according toclaim 1, wherein Y is fluorine or chlorine, and V is ##STR144## .[.6.The monoazo dye according to claim 1, wherein R¹ is --NHCONH₂..]..[.7.The monoazo dye according to claim 1, wherein Y is ##STR145## .[.8. Themonoazo dye according to claim 7, wherein E is ##STR146## .[.9. Themonoazo dye according to claim 1, wherein Y is ##STR147## .[.10. Themonoazo dye according to claim 1, wherein Y is ##STR148## and V isfluorine or chlorine..]..[.11. The monoazo dye according to claim 1,wherein Y is ##STR149## V is fluorine or chlorine, and R¹ is --NHCOCH₃,--NHCOCH₂ CH₂ COOH or --NHCOCH═CH--COOH..]..[.12. The monoazo dyeaccording to claim 11, wherein R¹ is --NHCOCH₂ CH₂ COOH or--NHCOCH═CH--COOH..]..Iadd.13. A water-soluble monoazo dye, wherein saiddye is a compound having the following formula: ##STR150## wherein X"'is --CH═CH₂ or --CH₂ CH₂ W wherein W is a leaving group removable byalkali;R^(2"') is hydrogen, lower alkyl or lower alkoxy; R^(1"') is--NHCOOH₂ CH₂ COOH or --NHCOCH═CHCOOH; P"' is chlorine or cyano; Q"' isfluorine or chlorine; U"' is fluorine or chlorine; wherein when P"' ischlorine, each of Q"' and U"' is fluorine, and when P"' is cyano, eachof Q"' and U"' is chlorine. .Iaddend..Iadd.14. A monoazo dye accordingto claim 13, having the formula in its free acid form: ##STR151##